CN104066800B - Resin blend - Google Patents

Resin blend Download PDF

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Publication number
CN104066800B
CN104066800B CN201280067787.2A CN201280067787A CN104066800B CN 104066800 B CN104066800 B CN 104066800B CN 201280067787 A CN201280067787 A CN 201280067787A CN 104066800 B CN104066800 B CN 104066800B
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resin
blend
chemical formula
difference
bed
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CN104066800A (en
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崔银株
柳真英
金宇星
刘兴植
李汉娜
崔贤
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LG Corp
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of resin blend and resin particle, this resin blend and resin particle can form hierarchy, and comprise: the first resin；And second resin, this second resin in main chain containing hydrophobic part and with described first resin surface at 25 DEG C can difference be 0.1 and 20mN/m, the invention still further relates to a kind of method preparing this resin blend and resin particle, and a kind of resin formed article with specific hierarchy.Described resin blend is possible not only to improve the mechanical performance of mechanograph and case hardness, and can also be demonstrated by any extra topical applying step of omission and shorten process time, raising productivity ratio and the advantage reducing production cost.

Description

Resin blend
Technical field
The application relates to resin blend, resin particle, uses them to prepare the method for resin formed article and resin molded Product.
Background technology
Plastic resin is prone to processing, has performance such as hot strength, elastic modelling quantity, thermostability and the impact resistance of excellence, And it is used for multiple use, such as in auto parts, the helmet, electric parts, spinning machine part, toy or pipeline.
Particularly, for home appliances, auto parts and toy resin due to direct body contact, therefore should be Eco-friendly, and there is the case hardness of excellence.But, typically, predetermined when making resin be externally exposed environment When time or longer time, resin by the oxygen in air, ozone or light degradation, thus easily can fade.Therefore, in order to improve Weatherability that resin is poor and relatively low intensity, generally use other spraying paint or electroplating process to resin.But, this spray paint Or electroplating process can reduce efficiency and the economic feasibility of plastic resin preparation process, and spraying paint or in electroplating process or produce Product may produce substantial amounts of harmful substance during disposing.
Therefore, multiple do not carrying out spraying paint or in the case of electroplating process, strengthening resin properties, such as scratch resistance, heat-resisting Property and the method for weatherability have been obtained for proposing.It has been proposed, for example, that one adds inorganic particulate to strengthen thing in resin Rationality can be such as wearability and the method for hardness.But, this method may reduce the processing characteristics of plastic resin, and adds Inorganic particulate is likely to result in the decline of impact strength and glossiness.
Summary of the invention
Technical problem
The application aim to provide a kind of resin blend, resin particle, use they prepare the method for resin formed article and Resin formed article.
Technical scheme
The one side of the application provides a kind of resin blend, and this resin blend comprises the first resin and in main chain Difference containing the hydrophobic part represented by chemical formula 1 and with described first resin surface energy at 25 DEG C is 0.1 to 20mN/ Second resin of m, and, this resin blend can form hierarchy.
[chemical formula 1]
In chemical formula 1, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is the number of 1 to 100.
The another aspect of the application provides a kind of resin particle, and this resin particle includes: core containing the first resin and containing the The shell of two resins, described second resin contains the hydrophobic part represented by chemical formula 1, and with described first resin at 25 DEG C Surface can difference be 0.1 to 20mN/m.
The another further aspect of the application provides a kind of resin formed article, and this resin formed article includes: the first resin bed；Described The second resin bed formed on first resin bed；And contain the first resin and the second resin and in first and second tree described Between lipid layer formed boundary layer, wherein, described second resin bed comprises the second resin, this second resin in main chain containing by The hydrophobic part that chemical formula 1 represents.
The another aspect of the application provides a kind of method preparing resin formed article, and the method includes: make above-mentioned resin altogether Mixed thing melts, and forms mixture of melts；It is processed with to described mixture of melts, forms hierarchy.
The another aspect of the application provides a kind of method preparing resin formed article, and the method includes: make above-mentioned resin particle Melted, form mixture of melts；It is processed with to described mixture of melts, forms hierarchy.
Hereinafter, by the exemplary with regard to the application, to resin blend, resin particle, they preparation trees are used Method and the resin formed article of fat mechanograph are described in more detail.
In this application, " blend " can be the mixture of at least two resin.The kind of described blend can be wrapped Include but be not particularly limited to, at least two resin being blended in a kind of substrate or at least two resin particle.Particularly, such as Fig. 1 Shown in, when at least two resin is blended in a kind of substrate, the compositions that comprises at least two resin 11 can be made Resin particle 10.Meanwhile, when blended at least two resin particle, as shown in Figure 2, at least two respectively can be contained a kind of resin Resin particle 20 and 21 be blended.Described resin can have different physical properties, and these physical properties can be surface Energy, melt viscosity or solubility parameters.
" melting process " refers to make resin blend melted under melt temperature (Tm) or higher temperature and form melt altogether Mixed thing, and use this mixture of melts to form the process of required mechanograph, this process is, such as injection-molded, extrusion molded, in Empty molding, transmission molding, sheet blowing, fibre spinning, calendering hot molding or foaming molding.
" resin formed article " refers to resin particle or the product formed by described resin blend, and this resin formed article can be But it is not particularly limited to, such as, auto parts, electric parts, machine parts, functional membrane, toy or pipeline.
" layer separation " may refer to substantially be set or be arranged in by the layer of a kind of resin formation substantially by difference tree On the layer that fat is formed.This means in substantially layer by a kind of resin formation, a kind of resin is also formed without sea-island structure, But be continuously present on the whole surface of a layer.Described sea-island structure, in whole resin blend, is distributed partly There is separated resin.It addition, " substantially ... formed " may refer to only exist a kind of resin in one layer or rich in one Plant resin.
According to the application, resin compound the resin formed article formed by melting process can have the machine of enhancing Tool and surface characteristic, and reduce cost and the time of preparation.Such as, the resin blend of the application can be by melting process Layering, and for be the most such as coated with electroplating process in the case of, preparation there is specific function (on such as surface High rigidity) resin formed article.
Described resin blend can be due to the physical property difference between first and second resin and/or the second resin Polydispersity index and genetic horizon separate.Herein, described physical property can be, such as, and surface energy, melt viscosity and solubility ginseng Number.But, although describe being blended of two kinds of resins in this application, but for it would be apparent to one of skill in the art that , three kinds or more kind can be had the resin alloy of different physical properties, carried out layer separation by melting process.
An exemplary according to the application, it is provided that a kind of resin blend, this resin blend bag Containing the first resin and with described first resin surface at 25 DEG C can the second resin that difference is 0.1 to 20mN/m, and, should Resin blend can form hierarchy.
Between first and second resin described surface at 25 DEG C can difference can be 0.1 to 20mN/m, 0.5 to 20mN/m, 1 to 20mN/m or 5 to 20mN/m.When the difference of surface energy is less than 0.1mN/m, the first and second resins easily mix, The second resin is made to be difficult to be transferred to surface, therefore, it is difficult to genetic horizon segregation phenomenon.It addition, when the difference of surface energy is more than During 20mN/m, the first and second resins may will not be bonded to each other and occur to separate or peel off.
The upper limit and/or the lower limit of the difference of described surface energy can be the selectable value in the range of 0.1 to 20mN/m, and can To depend on the physical property of the first resin.Particularly, when using the first resin to be used as by the second resin as matrix resin When functional resin is to strengthen the surface characteristic of the first resin, the second resin can be selected so that this first and second resin exists The difference of the surface energy at 25 DEG C is 0.1 to 20mN/m.In an example, can in view of the melt at the first and second resins altogether In mixed thing, the hydrophobicity of the second resin selects the difference of surface energy.
The described resin blend at first and second resins that difference is 0.1 to 20mN/m of 25 DEG C of lower surfaces energy can lead to Cross melting process and carry out layer separation.In an example, when by melted for the resin blend of this first and second resin and sudden and violent When being exposed in air, the first and second resins can separate due to hydrophobic difference.Especially since surface can be less than first Second resin of resin has a higher hydrophobicity, therefore this second resin be transferred and and air contact, be consequently formed towards Second resin bed of air.It addition, the first resin can contact with this second resin, and it is arranged on the face contrary with air. The layer between first and second resin is therefore, it can to occur in described resin blend to separate.
As an example of the application, described second resin can comprise hydrophobic part in main chain.When the second resin Main chain in when comprising hydrophobic part, can increase further the surface with the first resin can difference, but also layer can be improved The efficiency separated.
Described hydrophobic part can be represented by such as chemical formula 1.
[chemical formula 1]
In chemical formula 1, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is the number of 1 to 100.
Described alkyl can be but be not limited to: straight chain containing 1 to 16,1 to 12,1 to 6 or 1 to 4 carbon atom or Alkyl group.
Described n can pass through RaTo RdCarbon number purpose summation control.Such as, R is worked asaTo RdCarbon atom number Summation bigger time, n may be controlled to less number；And work as RaTo RdCarbon number purpose summation less time, n can control For bigger number.Such as, R is worked asaTo RdDuring all methyl, n can be 1 to 100,5 to 80,10 to 60,15 to 40 or 15 to 30 In the range of.But, work as RaTo RdDuring for different substituents besides methyl, the value of n may be controlled to and described substituent group The value that carbon number is identical.
It addition, described n can be such as integer or mark.In an example, when n is expressed as integer, it can be Refer to the value of the chemical formula 1 of a kind of molecule comprised in the second resin.In an example, when n is expressed as mark, it can be Refer to the meansigma methods of the chemical formula 1 of two or more molecules comprised in the second resin.
In the case of the hydrophobic part represented by chemical formula 1 is hydrophobic for the second resin offer, comprise this second resin Content can be, such as so that when carrying out melted with the first resin, genetic horizon separates.Although in the main chain of the second resin The content comprising the hydrophobic part represented by chemical formula 1 is relatively low, but can be that this second resin provides higher hydrophobicity.Example As, relative to described second resin of 100 weight portions, chemical formula 1 content of the hydrophobic part represented may be controlled to comprise 0.01 to 15 weight portion, 0.01 to 10 weight portion, 0.01 to 5 weight portion, 0.1 to 15 weight portion, 0.1 to 10 weight portion, 0.1 to 5 weight portions or 0.5 to 4 weight portion.In this range, the second resin easily can divide with the first resin in melting process From, and the surface layer of high rigidity can be formed on the surface of the first resin.
Can such as use the monomer represented by chemical formula 2, introduce by chemical formula 1 table in the main chain of described second resin The hydrophobic part shown.
[chemical formula 2]
In chemical formula 2, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is the number of 1 to 100.Separately Outward, X1And X2For hydrogen, alkyl containing 1 to 16 carbon atom or sulfydryl (-SH), and X1And X2In at least one be sulfydryl.This Place, described alkyl and n are explained in chemical formula 1.
In an example, chemical formula 2 weight average molecular weight of the monomer represented can be about 200 to 10000,300 to 9000,400 to 8000,500 to 7000,600 to 6000,700 to 5000,800 to 4000,900 to 3000 or 1000 to 2500. Therefore, it can the weight average molecular weight in view of the monomer represented by chemical formula 2 and control the n of chemical formula 1 or 2 suitably.
The monomer represented by chemical formula 2 can be, such as, and the polydimethylsiloxane of dimercapto end-blocking or single sulfydryl end-blocking Polydimethylsiloxane.
Described resin blend is segmented at least two layer.In an example, when by the two of molten resin blend When individual apparent surface is exposed in air, the resin blend of the first and second resins is segmented into three layers, such as institute in Fig. 3 The second resin bed/the first resin bed/the second resin bed shown.Meanwhile, when only a surface of molten resin blend being exposed Time in air, resin blend is segmented into two layers, the such as second resin bed/the first resin bed.It addition, when to comprising table When the resin blend of first, second, and third resin that face energy is different carries out melted, molten resin blend is segmented into five Individual layer, such as the 3rd resin bed/the second resin bed/the first resin bed/the second resin bed/the 3rd resin bed shown in Fig. 4.Separately Outward, when being exposed in air on the whole surface of molten resin blend, resin blend is layered in all directions, thus Form nucleocapsid structure as shown in Figure 5.
Another exemplary according to the application, it is provided that a kind of resin blend, this resin blend Comprising the first resin and the second resin, described second resin is at 100 to 1000s-1Shear rate and the adding of this resin blend At a temperature of work, the difference with the melt viscosity of described first resin is 0.1 to 3000pa*s.
At 100 to 1000s-1Shear rate and resin blend processing temperature under, first and second resin described it Between the difference of melt viscosity can be 0.1 to 3000pa*s, 1 to 2000pa*s, 1 to 1000pa*s, 1 to 600pa*s, 50 to 600pa*s, 100 to 600pa*s, 200 to 600pa*s or 250 to 550pa*s.When the difference of melt viscosity is less than 0.1pa*s, First and second resins easily mix, therefore, it is difficult to be easily layered；And when the difference of melt viscosity is more than 3000pa*s, First and second resins may will not bond and meeting is peeling-off.
The upper limit of the difference of described melt viscosity and/or lower limit can be the selectable value in the range of 0.1 to 3000pa*s, and And the physical property of the first resin can be depended on.Particularly, when using the first resin as matrix resin by the second resin During as functional resin to strengthen the surface characteristic of the first resin, the second resin can be selected so that this first and second tree Fat is at 100 to 1000s-1Shear rate and resin blend processing temperature under the difference of melt viscosity be 0.1 to 3000pa* s.In an example, can in view of in the mixture of melts of the first and second resins the mobile performance of the second resin select The difference of melt viscosity.
Described at 100 to 1000s-1Shear rate and resin blend processing temperature under the difference of melt viscosity be 0.1 The resin blend of the first and second resins to 3000pa*s can be layered because of the melt viscosity difference after melting process.Make For example, when the resin blend of this first and second resin is melted and is exposed in air, the first and second resins can Separate with the difference due to mobile performance.Especially since melt viscosity has higher less than the second resin of the first resin Mobile performance, therefore this second resin can be transferred and and air contact, be consequently formed towards air arrange the second tree Lipid layer.It addition, the first resin can be placed on the face contrary with air in the case of contacting with this second resin.Therefore, Layer separation between first and second resin in described resin blend can occur.
As the example of the application, described second resin can comprise and has predetermined or huge more than predetermined Organo-functional group.When introducing specific huge organo-functional group, the hydrodynamic volume of the second resin can be made to increase, thus There is lower melt viscosity.Therefore, in the resin introducing huge organo-functional group, can be easier in melting process There is above-mentioned layer segregation phenomenon in ground.The instantiation of described huge organo-functional group can be: containing 2 to 20,2 to 12,2 to 6, The alkyl of 3 to 20,3 to 12 or 3 to 6 carbon atoms, containing the alicyclic ring of 5 to 40,5 to 25 or 5 to 16 carbon atoms, and contains The aromatic ring of 6 to 40,6 to 25 or 6 to 16 carbon atoms.It is not particularly limited for having the functional group of hydrodynamic volume, but At least one in such organo-functional group can be comprised in the second resin.
Specifically, described huge organo-functional group can be, such as, the aliphatic functionality such as tert-butyl group, isobutyl group or Isopropyl, alicyclic ring functional group such as isobornyl or cyclohexyl, or aromatic ring functional group such as naphthyl, phenyl, anthryl or benzyl.
Melt viscosity refers to the shear viscosity (pa*s) according to specific processing temperature and shear rate (/s), and it can lead to Cross capillary flow to measure.
The shear rate applied when " shear rate " refers to be processed described resin blend, according to the side of processing Method, can control shear rate at 100 to 1000s-1Between.For the ordinary skill in the art, according to processing Method controls shear rate and is apparent from.
" processing temperature " refers to the temperature being processed described resin blend.Such as, this temperature refers to by resin When blend is in the melting process such as extruded or inject, the temperature that this melting process is used.Processing temperature can To be controlled according to the resin of melting process being applied to such as extrude or inject.Such as, the first resin is comprised when use During the resin blend of (ABS resin) and the second resin of being prepared by Tri-n-butyltin methacrylate monomer, processing temperature can be 210 to 240 DEG C.
Another exemplary according to the application, it is provided that a kind of resin alloy forming hierarchy Thing, this blend comprises the first resin, and is 0.001 to 10.0 (J/cm with the difference of the solubility parameters of described first resin3 )1/2The second resin.
Between first and second resin described, the difference of the solubility parameters at 25 DEG C can be 0.001 to 10.0 (J/cm3 )1/2, 0.01 to 5.0 (J/cm3)1/2, 0.01 to 3.0 (J/cm3)1/2, 0.01 to 2.0 (J/cm3)1/2, 0.1 to 1.0 (J/cm3 )1/2, 0.1 to 10.0 (J/cm3)1/2, 3.0 to 10.0 (J/cm3)1/2, 5.0 to 10.0 (J/cm3)1/2Or 3.0 to 8.0 (J/cm3 )1/2.This solubility parameters is the initial characteristic demonstrating deliquescent resin, and it depends on the polarity of each molecular resin, and And solubility parameters for various resins is commonly known.When the difference of solubility parameters is less than 0.001 (J/cm3)1/2Time, first Resin is prone to and the second mixed with resin, therefore, it is difficult to genetic horizon separates；And when the difference of solubility parameters is more than 10.0 (J/cm3)1/2 Time, the first and second resins may will not bond and meeting is peeling-off.
The upper limit of the difference of described solubility parameters and/or lower limit can be at 0.001 to 10.0 (J/cm3)1/2In the range of can Choosing value, and the physical property of the first resin can be depended on.Particularly, when using the first resin as matrix resin by When two resins are used as functional resin to strengthen the surface characteristic of the first resin, the second resin can be selected so that this first with Between second resin, the difference of the solubility parameters at 25 DEG C is 0.001 to 10.0 (J/cm3)1/2.In an example, Ke Yijian In the mixture of melts at the first and second resins, the miscible performance of the second resin selects the difference of solubility parameters.
Described at 25 DEG C the difference of solubility parameters be 0.001 to 10.0 (J/cm3)1/2The resin of the first and second resins Blend can carry out layer separation by melting process.In an example, when by the resin of this first and second resin altogether When mixed thing melts and is exposed in air, the first and second resins can separate due to the degree of miscible performance.Particularly, exist It is 0.001 to 10.0 (J/cm relative to the difference of the solubility parameters of the first resin at 25 DEG C3)1/2The second resin possibly cannot be with This first mixed with resin.Therefore, when the second resin additionally has less than the surface tension of the first resin or melt viscosity, this is years old Two resins can be transferred and and air contact, be consequently formed towards air arrange the second resin bed.It addition, the first resin can To contact with this second resin, and it is arranged on the face contrary with air.Therefore, at first and second of described resin blend Can separate with genetic horizon between resin.
According to another exemplary of the application, the PDI of described second resin can be 1 to 2.5,1.3 to 2.5,1.5 to 2.5 or 1.7 to 2.5.The upper and lower bound of the PDI of this second resin can be the selectable value of 1 to 2.5.
When the PDI of the second resin is higher than 2.5, the first resin and the second resin are likely to be due to low-molecular-weight and easily mix Close, or the mobile performance of the second resin is likely to be due to high molecular and declines, cause being difficult to layer and separate.
According to another exemplary of the application, the weight average molecular weight of the second resin of described resin blend (Mw) can be 30,000 to 200,000,50,000 to 200,000,80,000 to 200,000,50,000 to 150,000,80, 000 to 150,000,50,000 to 120,000 or 80,000 to 120,000.The upper limit of the weight average molecular weight of this second resin and Lower limit can be the selectable value in the range of 30,000 to 200,000.
When described weight average molecular weight is less than 30,000, the first and second resins easily mix；And when described Weight-average molecular When amount is more than 200,000, the mobile performance of the second resin declines, thus is difficult to genetic horizon and separates.
It addition, according to another exemplary of the application, the glass transition temperature of described second resin (Tg) can be able to be higher than the difference of the glass transition temperature between described first resin, and this first and second resin 10, more than 20 or 23 DEG C.The maximum of the difference of the glass transition temperature between this first and second resin can be but not It is particularly limited in less than 150 DEG C.
When the glass transition temperature of the second resin exceeds more than more than 10 DEG C than the first resin, glass transition temperature The second higher resin is arranged on the outside of resin formed article, thus enhances the hardness on surface to a great extent.
Particularly, as the example of the application, combine (hydrogen-binding) donor of hydrogen when the second resin comprises During with receptor, this second resin can have higher glass transition temperature, so that finally moulding the case hardness of product Can be further improved.
In this manual, as the donor of described combination hydrogen, it is possible to use comprise the functional group of the hydrogen being combined with N or O Or residue and be not particularly limited, and can be such as OH base, NH2Base, NHR base, COOH base, CONH2Base, NHOH base, or NHCO key, NH key, CONHCO key or the residue of NH-NH key in molecule.
It addition, in this manual, the receptor of described combination hydrogen can be the functional group containing N or O or residue does not has spy Do not limit, such as OH base, OR base, NH2Base, NHR base, NR2Base, COOH base, COOR base, CONH2Base, CONR2Base, NHOH base, NROR base, or NHCO key in molecule, NRCO key, O key, NH key, NR key, COO key, CONHCO key, CONRCO key, NH-NH Key, NR-NH key or the residue of NR-NR key.Herein, R can be aliphatic hydrocarbon, aromatics hydrocarbons and their derivates, such as, contain 1 to 16 Or the aliphatic hydrocarbon of 1 to 9 carbon atom, aromatics hydrocarbons and their derivates containing 5 to 30 or 5 to 16 carbon atoms.The most special Being confined to theory, great majority combine the donor of hydrogen and can serve as combining the receptor of hydrogen.The donor of described combination hydrogen provide with The hydrogen that the atom that electronegativity is bigger is connected, meanwhile, the atom that part electronegativity is bigger is also used as combining the receptor of hydrogen.So And, there is also picture-(NH4)+Base is so used only as combining the functional group of the donor of hydrogen.
When described second resin comprises donor and the receptor combining hydrogen simultaneously, this second resin can demonstrate glass The raising of glass temperature.
In an example, donor and the receptor of described combination hydrogen may reside in a kind of resin.One comprises combination The donor of hydrogen and the resin of receptor by making by the monomer comprising donor and the receptor combining hydrogen, or can comprise and combine hydrogen The monomer of donor and the resin polymerization that constitutes of the monomer that comprises the receptor combining hydrogen and prepare.Herein, it is possible to use Yi Zhonghuo At least two monomer.
In another example, donor and the receptor of described combination hydrogen may reside in different types of resin.That is, may be used Resin obtained by the monomer comprising the donor combining hydrogen polymerization will be made to obtain with making the monomer comprising the receptor combining hydrogen be polymerized Resin alloy, and be included in the second resin.Herein, it is possible to use one or both or more kinds of monomer.It addition, described In second resin, when combine the donor of hydrogen and receptor presented in one or both or more kinds of resin time, it is also possible to bag Containing without combining the donor of hydrogen and/or the resin of receptor.
This combines hydrogen the monomer of the donor and/or receptor that combine hydrogen can be provided can to comprise at least one for the second resin Donor and/or the functional group of receptor or residue, for example, at least two or three functional groups or residue.
The described monomer comprising the donor and/or receptor that combine hydrogen can be but is not particularly limited to: vinyl ethers, such as Methyl vinyl ether or ethyl vinyl ether；Nitrogen containing monomer, such as (methyl) acrylamide, N-replace (methyl) acrylamide or N, N-replace (methyl) acrylamide；Vinyl acetate；Hydroxyl monomer, such as (methyl) acrylic acid hydroxy alkyl ester；Containing carboxyl Monomer, such as (methyl) acrylic acid, 2-(methyl) acryloxyacetic acid, 3-(methyl) acryloxy propionic, 4-(methyl) Acryloxy butanoic acid, acrylic acid dimer, itaconic acid, maleic acid or maleic anhydride；Or heterocyclic compound, such as vinyl Ketopyrrolidine, acryloyl morpholine or comprise the monomer of 2-urea groups-4-pyrimidone.
Meanwhile, described first resin is the resin of the main physical property determining required molding product, and can basis Kind and the process conditions of required molding product select.As such first resin, it can be common synthesis tree Fat and be not limited to, such as, styrene resin such as acrylonitrile-butadiene-styrene (ABS) (ABS) resinoid, polystyrene type tree Fat, acrylonitrile-styrene-acrylic ester (ASA) resinoid or styrene butadiene styrene block copolymer (SBS) resinoid；Poly- Olefine kind resin such as high-density polyethylene vinyl resin, low density polyethylene vinyl resin or polypropylene-based resin；Thermoplastic elastomer (TPE) Such as esters thermoplastic elastomer (TPE) or olefin hydrocarbons thermoplasticity elastic body；Polyoxyalkylene resinoid such as polyformaldehyde resinoid or polyoxyethylene Resinoid；Polyester resin such as polyethylene terephthalate resinoid or polybutylene terephthalate (PBT) resinoid；Poly- Vinyl chloride resin；Polycarbonate resin；Polyphenylene sulfide resinoid；Vinyl alcohol resin；Polyamide-based resin；Acrylate Resinoid；Engineering plastics；The copolymer of above-mentioned resin, or their mixture.Described engineering plastics are to show excellence Plastics both mechanically and thermally.It is, for example possible to use polyether-ketone, polysulfones and polyimides are as described engineering plastics.At one In example, it is possible to use the copolymer of styrene resin and acrylic resin is as described first resin.
Described second resin refers to that above-mentioned physical property is different from the first resin, and can be the table of required molding product Face provides superior mechanical properties and the resin of more high surface hardness.
In an example, described second resin can be to comprise the monomer represented by chemical formula 2 as mentioned above as poly- Close the polymer of unit.Such as, the monomer that should be represented by chemical formula 2 can be included in the case of another kind of monomer copolymerization In second resin.The concrete kind of the resin comprised in described second resin can be but be not limited to, such as, and (methyl) third Olefin(e) acid esters resin, epoxylite, oxetanes resinoid, isocyanates resinoid, fluorine-type resin or they be total to Polymers.
In an example, when the second resin comprises (methyl) acrylic resin, described represented by chemical formula 2 Monomer can be included in this second resin in the case of being polymerized with (methyl) acrylic monomer.Such (methyl) third Alkene acrylic monomer can be but be not limited to, such as, and (methyl) alkyl acrylate such as (methyl) acrylic acid methyl ester., (methyl) third Olefin(e) acid ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) propylene are misery Ester, (methyl) lauryl acrylate or (methyl) octadecyl acrylate；Or (methyl) glycidyl acrylate.
In another example, when comprising epoxylite in the second resin, the described monomer represented by chemical formula 2 can With with for providing the monomer of epoxylite to be included in the case of being polymerized in this second resin.Described epoxylite can Think but be not limited to: bisphenol type such as bisphenol A-type, bisphenol-f type, bisphenol S type and their hydrogenated products；Phenol aldehyde type such as phenol Phenol aldehyde type or cresol novolak type；Nitrogenous ring-like such as triglycidyl isocyanurate type or hydantoin type；Alicyclic type；Fat Race's type；Aromatics type such as naphthalene type or biphenyl type；Glycidyl type such as diglycidyl ether type, glycidic amine type or ethylene oxidic ester Type；Double ring type such as dicyclopentadiene-type；Ester type；Or Etheric ester type.
In another example, when the second resin comprises oxetanes resinoid, described represented by chemical formula 2 Monomer can be included in the case of being polymerized with the oxetane monomer containing at least one oxetanes ring this second In resin.Such oxetane monomer can be but be not limited to, such as, and Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy Methoxyl group) methyl] benzene, two [1-ethyl (3-oxetanylmethoxy)] methyl ether, phenol novolac oxetanes, terephthalate two Oxetanes (terephthalate bisoxet-ane) or biphenylene dioxetane (biphenylene bisoxetane)。
It addition, in another example, when the second resin comprises isocyanates resinoid, described by chemical formula 2 table The monomer shown can be included in this second resin in the case of being polymerized with the monomer containing NCO.Use-case can be made If '-diphenylmethane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) or isophorone diisocyanate (IPDI) are as this Plant the monomer containing NCO, but the application is not limited thereto.
It addition, in another example, when the second resin comprises fluorine-type resin, the described list represented by chemical formula 2 Body can be included in this second resin in the case of being polymerized with fluorine class monomer.Such as tetrafluoroethene, trifluoro chlorine can be used Ethylene, Fluorinated vinylidene (fluorinated vinylidene) or fluorinated vinyl (fluorinated vinyl) conduct This fluorine class monomer, but the application is not limited thereto.
The content of the described monomer represented by chemical formula 2 can be suitably controlled in can provide hydrophobicity for the second resin And can with first resin layering in the range of.In an example, relative to second resin of aggregating into of 100 weight portions All monomers, the content of the monomer that should be represented by chemical formula 2 can control 0.01 to 15 weight portion, 0.01 to 10 weight portion, 0.01 to 5 weight portion, 0.1 to 15 weight portion, 0.1 to 10 weight portion, 0.1 to 5 weight portion or 0.5 to 4 weight portion.
Aforementioned statement " by (methyl) acrylate, epoxy, oxetanes, isocyanates or fluorine-type resin or they Copolymer be used as the second resin " refer to by above-mentioned resin be used as the second resin Primary resins.Therefore, in an example, Can use by polymer obtained by the polymerization of following monomer mixture as the second resin, this monomer mixture comprises can be provided The monomer of Primary resins and the monomer represented by chemical formula 2.In another example, it is possible to use gathered by following monomer mixture Polymer obtained by conjunction as the second resin, this monomer mixture also comprise can to the described monomer providing Primary resins and The monomer represented by chemical formula 2 introduces huge organo-functional group and/or combines the donor of hydrogen and the monomer of receptor.
Described can introduce huge organo-functional group monomer can be, such as, (methyl) tert-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) isopropyl acrylate, (methyl) isobornyl acrylate, (methyl) cyclohexyl acrylate, (first Base) acrylic acid naphthalene ester, (methyl) phenyl acrylate, (methyl) acrylic acid anthracene ester or (methyl) benzyl acrylate.
Further, it is possible to use the monomer of above example is as the described monomer that can introduce donor and the receptor combining hydrogen.
Relative to the first resin of 100 weight portions, described resin blend can comprise 0.1 to 50 weight portion, such as 1 to Second resin of 20 weight portions, 1 to 15 weight portion or 5 to 15 weight portions.
When the second resin-phase for 100 weight portion the first resins content less than 0.1 weight portion time, will not be separated Phenomenon；And when the content of the second resin is more than 50 weight portion, make preparation cost increase due to the high cost of the second resin.
Described resin blend can be prepared as resin particle by extrusion.As shown in Figure 6, this resin blend is used The resin particle of preparation can be with cambium layer, wherein the first centrally disposed place of resin, and the second resin and the layering of the first resin, and It is arranged at the shell of this resin particle.
According to the exemplary of the application, resin particle includes: comprise the core of the first resin；With comprise the second resin Shell, described second resin in main chain containing the hydrophobic part that represented by chemical formula 1, and with described first resin at 25 DEG C Under surface can difference be 0.1 to 20mN/m.
[chemical formula 1]
In chemical formula 1, RaTo RdAnd n is as defined above.It addition, as it has been described above, the first and second resins can have There is different physical propertys.Such as, the difference of described first and second resins surface energy at 25 DEG C can be 0.1 to 20mN/ M, at 100 to 1000s-1Shear rate and resin particle processing temperature under the difference of melt viscosity can be 0.1 to 3000pa* S, and the difference of the solubility parameters at 25 DEG C can be 0.001 to 10.0 (J/cm3)1/2.It addition, the PDI of described second resin Can be 1 to 2.5, and the weight average molecular weight of this second resin can be 30,000 to 200,000.Additionally, described second tree The glass transition temperature of fat can be higher than the glass transition temperature between described first resin, and this first and second resin The difference of degree can be 10 DEG C to 150 DEG C.
Therefore concrete kind and the physical property of described first and second resins as it has been described above, describe in detail omission.
Meanwhile, according to another exemplary of the application, it is provided that a kind of preparation has hierarchy The method of resin formed article.The method may include that the blend making the first resin and the second resin melts, and is formed melt blended Thing；It is processed with to described mixture of melts, forms hierarchy.
The physical property difference being as noted previously, as between first and second resin, therefore at molten resin blend During can be with genetic horizon segregation phenomenon, and due to this layer segregation phenomenon, can be to resin particle or the surface of molding product Carry out selectively applied and without single additional procedure.
Particularly, second resin of the application is by introducing the hydrophobic part represented by chemical formula 1 and permissible in chain linked to owner There is lower surface and to improve layering efficiency, and thus can provide that the second resin (such as high hardness resin) is easier Be arranged at surface so that mechanical performance and surface characteristic obtain strengthen molding product.
Meanwhile, described melting process can be carried out under shear stress, and can be but be not limited to extrusion and/or note Penetrate.
According to another exemplary of the application, described resin blend can be melted by such as extrude Process and be prepared as resin particle.Such as, as it has been described above, in the resin blend comprising the first and second resins, due to second The hydrophobicity of resin be higher than the first resin, therefore this second resin be transferred and and air contact, be consequently formed the table of resin particle Surface layer；And the first resin is arranged on the center of this resin particle, it is consequently formed core.Furthermore it is possible to described resin blend is squeezed Go out for resin particle, may then pass through the melting process such as injected and the preparation of this resin particle is become molding product.Meanwhile, may be used With the melting process by such as injecting, directly prepared molding product by described resin blend.
In the melting process of described resin blend, according to the kind of the first and second resins, temperature can be carried out Change.
In the described method preparing resin formed article, it is also possible to including: make by molten resin blend prepared The molten product solidification of product, i.e. this resin blend.Described solidification can be, such as heat cure or ultraviolet curing.It addition, It will be apparent to one of ordinary skill in the art that, can the most chemically or physically process.
Meanwhile, the described method preparing resin formed article can also include: before making resin blend melted, preparation the Two resins.As it has been described above, the second resin can select according to the first resin, and the second selected resin can be The surface layer of resin formed article provides specific function, such as high rigidity.Can use any by making monomer polymerization prepare The common methods of resin prepares the second resin, and described method can be, such as mass polymerization, solution polymerization process, suspension gather Legal or emulsion polymerization.
The preparation of described second resin may include that the monomer by providing the hydrophobic part that can introduce chemical formula 1 (monomer such as represented by chemical formula 2) and can provide the monomer dispersion of monomer of Primary resins in reaction dissolvent, at this It is blended with at least one additive in chain-transferring agent, initiator and dispersion stabilizer in reaction dissolvent, Yi Ji 40 DEG C or higher than making blend be polymerized at 40 DEG C.
Reaction medium can be that any known conventional does not has for the medium preparing synthetic resin, polymer or copolymer Limit.Example as this reaction medium, it is possible to use methyl ethyl ketone, ethanol, methyl iso-butyl ketone (MIBK), distilled water or they The mixture of middle at least two.
The chain-transferring agent in above-mentioned reaction dissolvent can be added can be but be not limited to: alkyl hydrosulfide such as normal-butyl sulfur Alcohol, n-dodecyl mercaptan, tertiary lauryl mercaptan or isopropyl mercaptan；Aryl mercaptan such as phenyl mercaptan, naphthyl mercaptan or benzyl Base mercaptan；Halogen compounds such as carbon tetrachloride；Or aromatic compounds such as α-methyl styrene dimer or α-ethyl styrene Dimer.
Described initiator can be that known conventional polymerization initiator in suspension polymerization is not particularly limited, example As, peroxide such as caprylyl peroxide, decanoyl peroxide or lauroyl peroxide；Or azo compound such as azo two isobutyl Nitrile or azo pair-(2,4-dimethyl)-valeronitrile.
The dispersion stabilizer in above-mentioned reaction medium can be included in can be but be not particularly limited to: organic dispersing agent is such as Polyvinyl alcohol, polyolefin-maleic acid, cellulose；Or inorganic dispersant such as tricalcium phosphate.
Details for described first and second resins and hydrophobic part has been carried out describing, and therefore will omit in detail Explanation.
Meanwhile, according to another exemplary of the application, resin formed article may include that the first resin bed； Second resin bed, this second resin bed is formed on described first resin bed；And boundary layer, this boundary layer contain the first resin and Second resin, and formed between first and second resin bed described.Herein, described second resin bed comprises containing by chemistry Second resin of the hydrophobic part that formula 1 represents.
[chemical formula 1]
In chemical formula 1, RaTo RdAnd n is as defined above.
By comprising the first resin and there is different physical properties and containing the hydrophobic part represented by chemical formula 1 in main chain The resin formed article prepared of the resin blend of the second resin can such as form hierarchy, in this hierarchy, One resin bed is arranged on inside, and the second resin bed is formed on the surface of resin formed article.
The structure of above-mentioned resin formed article, the i.e. first resin bed and the second resin bed are separated and the second resin bed by boundary layer The structure being externally exposed, not known routine techniques but a kind of new technique.It is special that this structure can not carry out strengthening surface Property coating or painting process, reduce preparation time and preparation cost, and improve the productivity of end product.This structure cannot Formed by extrusion or injection ordinary resin, and be difficult to obtain according to the effect of this structure.
Especially since described resin formed article employs comprises the hydrophobic part that represented by chemical formula 1 in main chain Second resin is to improve layering efficiency, and therefore the case hardness of this resin formed article can obtain extra raising.
Described " the first resin bed " can mainly comprise the first resin, in that case it can be decided that the physical property of molding product, and Can be arranged in resin formed article.It addition, described " the second resin bed " can mainly comprise the second resin, tree can be arranged on Fat mechanograph is peripheral, and can be the specific function of surface offer of molding product.
Details for described first and second resins and hydrophobic part has been carried out describing, and therefore will omit in detail Explanation.
Meanwhile, described resin formed article can be included between first and second resin bed and formed and comprise first and second The boundary layer of the mixture of resin.Described boundary layer can be formed for use as boundary between first and second resin bed separate Face, and comprise the mixture of the first and second resins.This mixture can be containing the first and second trees physically or chemically combined Fat, and the first and second resin beds can be combined by this mixture.
As it has been described above, described resin formed article can include the first and second resin beds by this boundary layer separately, and The structure that second resin bed is externally exposed.Such as, this molding product can have the first resin bed, boundary layer and the second resin The structure that is sequentially stacked of layer, and interface and the second resin be stacked in the above and below structure of the first resin.It addition, this tree Fat mechanograph can include following structure, wherein, multiple stereoscopic type (the most spherical, circular, polygon or platelet-type) First resin bed is surrounded successively by interface and the second resin bed.
The layer segregation phenomenon demonstrated in described resin formed article, is owing to applying physical property different specific One and second resin prepare this resin formed article and cause.This different physical property includes surface energy, melt viscosity And solubility parameters.Details about physical property difference is described above.
Meanwhile, the first and second resin beds of sample and boundary layer can be carried out low-temperature impact test, the most permissible Use the break surface of THF this sample of vapor etch, and use SEM to confirm.The thickness measure of each layer includes: use Thin slice chopper and slicer, forms smooth cross section with diamond knife cutting sample；And use can with the first resin-phase ratio More selectively dissolve the solution of the second resin, the cross section that this is smooth is etched.The dissolving of the cross section being etched Degree changes with the content of the first and second resins, and when using SEM to observe this cross section more than surface under 45 ° Time, due to shading value difference and it is observed that the first and second resin beds, boundary layer and surface, such that it is able to measure every The thickness of individual layer.In this application, it is alternatively that be easier to dissolve to property the solution of the second resin, employ 1,2-dichloroethanes Solution (10vol%, in EtOH), but higher than the solution of the first resin, spy is not had for any dissolubility to the second resin Do not limit, and choosing can be suitably carried out according to the kind of the second resin with forming by those of ordinary skill in the art Select.
Relative to described second resin bed and the gross thickness of boundary layer, the thickness of this boundary layer can be 0.01 to 95%, 0.1 to 70%, 0.1 to 50%, 5 to 50%, 10 to 50%, 15 to 50% or 20 to 50%.When the thickness of boundary layer is second The gross thickness of resin bed and boundary layer 0.01 to 95% time, owing to the interface bond strength between first and second resin bed is excellent Different, therefore the two layer is all without peeling-off, and can strengthen the surface produced by the second resin bed to a great extent Characteristic.On the other hand, when boundary layer and the second resin bed were compared thin, owing to the combination between first and second resin bed is strong Degree declines, and therefore the two layer is all it may happen that peel off；And when boundary layer is blocked up, the second resin bed the surface characteristic produced Reinforced effects may be less obvious.
Relative to whole resin formed articles, the thickness of described second resin bed can be 0.01 to 60%, 0.01 to 40%, 0.01 to 20%, 0.01 to 10%, 0.01 to 5%, 0.01 to 3% or 0.1 to 3%.When the thickness of the second resin bed exists Time in particular range, can be that the surface of molding product provides the case hardness or scratch resistance strengthened.When the second resin bed When thickness is too small, it is difficult to fully strengthen the surface characteristic of molding product；And when the thickness of the second resin bed is excessive, be likely to be due to The mechanical performance of functional resin self embodies and makes the mechanical performance of the first resin change on resin formed article.
For the physical property difference between described first and second resins, this first and second resin and this second tree The details of the hydrophobic part comprised in fat has been carried out describing, and therefore will omit relevant explanation.
Meanwhile, according to another exemplary of the application, it is provided that a kind of resin formed article, this resin mold Goods include the first resin bed, and the second resin bed formed on described first resin bed.Pass through infrared spectrophotometer (IR) on the surface of described second resin bed, detect the component of the first resin bed, and this second resin bed is included in main chain In containing the second resin of hydrophobic part represented by chemical formula 1.
The structure of above-mentioned molding product, i.e. detects first by infrared spectrophotometer on the surface of the second resin bed The structure of resin bed component, not known routine techniques but a kind of new technique, and in coating process, be generally difficult to The component of the first resin bed is detected on the surface of the second resin bed.
Herein, the surface of described second resin bed refers to be externally exposed (such as air) and non-contact the first resin bed Surface.
For the physical property difference between described first and second resins, this first and second resin and this second tree The details of the hydrophobic part comprised in fat has been carried out describing, and therefore will omit relevant explanation.
It addition, in this manual, the physical property difference between first and second resin described may refer to first with Physical property difference between second resin or between first and second resin bed.
It addition, according to another exemplary of the application, it is provided that comprise the vapour of described resin formed article Car part, the helmet, electric parts, spinning machine part, toy or pipeline.
Beneficial effect
According to the application, it is provided that a kind of resin blend, resin particle, use the method that they prepare resin formed article And the resin formed article prepared by the method, described resin blend can strengthen the mechanical performance of molding product and surface is hard Degree, and in the case of not using additional surface coating, it is possible to demonstrate and shorten process time, raising productivity ratio and reduce system The effect of standby cost.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the resin blend of an example as the application；
Fig. 2 is the schematic diagram of the resin blend of another example as the application；
Fig. 3 is being formed by the resin blend comprising the first resin and the second resin of an example as the application The schematic diagram of hierarchy；
Fig. 4 is being total to by the resin comprising the first resin, the second resin and the 3rd resin of an example as the application The schematic diagram of the hierarchy that mixed thing is formed；
Fig. 5 is the schematic diagram of the hierarchy of the another aspect as the application；
Fig. 6 is containing core and the schematic diagram of the resin particle of shell；
Fig. 7 is the SEM image of the layering cross section of the molding product of preparation in embodiment 3；
Fig. 8 is the SEM image of the cross section of the molding product of preparation in comparative example 1.
Detailed description of the invention
Hereinafter, with regard to embodiment, the application will be described in more detail.The following examples are provided to be only used for illustrating Bright the application, but scope of the present application is not limited to the following examples.
The measurement of glass transition temperature
Differential scanning calorimetry (DSC) (DSC823e, Mettler-toledo) is used to measure glass transition temperature.More specifically and Speech, will be contained in measurement apparatus containing the aluminum dish of 1mg the first resin sample or the second resin sample, and at-50 to 300 DEG C (10 DEG C/min, 2 times circulation) under measure glass transition temperature.
The measurement of surface energy
According to Owens-Wendt-Rabel-Kaelble method, Drop Shape Analyzer (DSA100, KRUSS) is used to survey Scale face energy.
More specifically, by the first or second resin with 10wt% be dissolved in methyl ethyl ketone and methyl iso-butyl ketone (MIBK) (2: 1) in blend solution, and rod is coated on cellulose triacetate (TAC) film.It addition, by the TAC film after coating at 90 DEG C of baking ovens In be dried 5 minutes.
After being dried (or solidification), the surface of this coating drips 10 deionized waters and diiodomethane, and obtain and connect The meansigma methods of feeler.This meansigma methods is substituted into Owens-Wendt-Rabel-Kaelble method, thus tries to achieve surface energy.
The measurement of melt viscosity
Capillary rheometer 1501 (Gottfert) is used to measure melt viscosity.
More specifically, after being connected on cylinder by capillary tube die head (capillary die), pour first or into Two resins are to be filled with 3 times.It addition, at 100 to 1000s-1Shear rate and the processing temperature of 240 DEG C under measure shear viscous Degree (pa*s).
Polydispersity index (PDI) and the measurement of weight average molecular weight (Mw)
Using gel permeation chromatography (GPC) to measure polydispersity index, condition is as follows.
-device: 1200 series, Agilent Technologies
-chromatographic column: 2 PL gel mixed B, Polymer Laboratories
-solvent: THF
-column temperature: 40 DEG C
-sample solubility: 1mg/mL, 100L sample introduction
-standard substance: polystyrene (Mp:3900000,723000,316500,52200,31400,7200,3940,485)
Use ChemStation (Agilent Technologies) conduct to analyze program, and divided by gpc measurement weight average Son amount (Mw) and number-average molecular weight (Mn), thus, calculated polydispersity index by weight-average molecular weight/number-average molecular weight (Mw/Mn) (PDI)。
The observation of cross section
The sample of embodiment and comparative example is carried out low-temperature impact test, uses the THF steam fracture table to each sample Face is etched, and then uses SEM to observe the cross section of layering.Meanwhile, use thin slice slicing device (Leica EM FC6), use Diamond knife cuts embodiment and the sample of comparative example at-120 DEG C and prepares smooth cross section, to measure the first of layering Resin bed, the second resin bed and the thickness of boundary layer.The cross-section parts of the sample comprising smooth cross section is immersed in 1,2- In dichloroethane solution (10vol%, in EtOH), etching 10 seconds, then clean with distilled water.This cross section is etched Part changes with the content of the first and second resins, and uses SEM to observe.That is, when seeing under more than surface 45 ° When examining described cross section, the first and second resin beds and boundary layer can be observed according to the difference of shading value, it is possible to Measure the thickness of each layer.
Measure the test of pencil hardness
Use pencil hardness test meter (Chungbuk Tech), under the permanent load of 500g, measure embodiment and compare The pencil hardness of the sample surfaces of example.In the case of standard pencil (Mitsubishi) is replaced by 9H by 6B, with 45 ° to table Swiping in face, observes the change (ASTM3363-74) on surface.Measurement result be repeat 5 times test try to achieve average Value.
Measure the test of intensity
The intensity of the sample of embodiment and comparative example is measured according to ASTM D256.Specifically, shock machine is used (Impact104, Tinius Olsen), measures the sample by making to be carved with V-notch towards pendulum hammer sword destroyed required Energy (Kg*cm/cm).The sample of 1/8 " and 1/4 " is respectively carried out 5 measurements, and tries to achieve meansigma methods.
By the surface analysis of infrared spectrophotometer
Use is equipped with Varian FTS-7000 spectrophotometer (Varian, USA) and mercury cadmium telluride (MCT) detector UMA-600 infrared microscope is analyzed, and uses Win-IR PRO3.4 software (Varian, USA) to carry out spectral measurement and data Processing, condition is as follows.
-refractive index is germanium (Ge) atr crystal of 4.0
-by attenuated total reflectance (ATR), at 8cm-1Spectral resolution under, with 4000cm-1To 600cm-1Mid-infrared Spectrum carries out 16 scanning
-internal reference wave band (internal reference band): the carbonyl of acrylate (C=O str. ,～ 1725cm-1)
The intrinsic component of the-the first resin: adiene cpd [C=C str. (～1630cm-1) or=C-H face outside vib. (～970cm-1)]
Calculate peak strength ratio [IBD(C=C)/IA] and [I (C=O)BD(outside face)/IA(C=O)], and at a sample Zones of different repeats 5 spectral measurements, thus calculates meansigma methods and standard deviation.
Embodiment 1
The preparation of (1) first and second resin and the measurement of physical property
Use by methyl methacrylate, the acrylonitrile of 7wt%, the butadiene of 10wt% and the benzene of 23wt% of 60wt% The thermoplastic resin of ethylene composition is as the first resin.In order to prepare the second resin, using 1500g distilled water and 4g as dispersant 2% polyvinyl alcohol water solution add in 3L reactor and dissolve.It follows that it is possible to additionally incorporate 792g methyl in this reactor The polydimethylsiloxane (PDMS, Mw:1670) of acrylic acid methyl ester., 8g dimercapto end-blocking, 1.6g are as positive the ten of chain-transferring agent Dialkyl group mercaptan and 2.4g are as the double methyl pentane nitrile of azo of initiator, and blended under agitation under 400rpm.Blend is existed At 60 DEG C, reaction is subsequently cooled to 30 DEG C to be polymerized, thus prepares second resin (A) of pearl type for 3 hours.It follows that will This second resin (A) uses distilled water wash three times, dehydration, is dried the most in an oven.
The difference of the surface energy between described first resin and the second resin (A) is 12mN/m, and the difference of melt viscosity is 325pa*s, the glass transition temperature of the first resin is 70 DEG C, and the glass transition temperature of the second resin (A) is 102 DEG C, by It is 100K that GPC records the weight average molecular weight of the second resin (A), and polydispersity index (PDI) is 2.1.
(2) preparation of resin blend and the measurement of physical property
Described first resin of 90 weight portions and described second resin (A) of 10 weight portions are blended, and use twin screw Extruder (Leistritz) is extruded at 240 DEG C, thus prepares resin particle.It addition, use EC100 Φ 30 syringe (ENGEL), by described resin particle at 240 DEG C of hemostasis, the resin formed article sample 1 that thickness is 3200 μm is prepared.At this sample In, the thickness of the second resin bed is 19 μm, and the thickness of boundary layer is 8 μm, and pencil hardness is H, at IZOD1/8 " in the case of strong Degree is for 9kg*cm/cm, at IZOD1/4 " in the case of intensity be 9kg*cm/cm, and observed a layer segregation phenomenon.
Embodiment 2
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (B) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use the polydimethylsiloxane (Mw:1670) of 784g methyl methacrylate and 16g dimercapto end-blocking to substitute 792g methyl methacrylate and the polydimethylsiloxane (Mw:1670) of 8g dimercapto end-blocking.
The difference of the surface energy between described first resin and the second resin (B) is 14mN/m, and the difference of melt viscosity is 340pa*s, the glass transition temperature of the second resin (B) is 101 DEG C, GPC the weight average molecular weight recording the second resin (B) is 100K, polydispersity index (PDI) is 2.2.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 2 that thickness is 3200 μm, difference is: make With described second resin (B).In this sample, the thickness of the second resin bed is 36 μm, and the thickness of boundary layer is 27 μm, and pencil is hard In the case of degree is for H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, and And observed a layer segregation phenomenon.
Embodiment 3
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (C) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use the polydimethylsiloxane (Mw:1670) of 776g methyl methacrylate and 24g dimercapto end-blocking to substitute 792g methyl methacrylate and the polydimethylsiloxane (Mw:1670) of 8g dimercapto end-blocking.
The difference of the surface energy between described first resin and the second resin (C) is 15mN/m, and the difference of melt viscosity is 350pa*s, the glass transition temperature of the second resin (C) is 99 DEG C, GPC the weight average molecular weight recording the second resin (C) is 100K, polydispersity index (PDI) is 2.2.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 3 that thickness is 3200 μm, difference is: make With described second resin (C).In this sample, the thickness of the second resin bed is 43 μm, and the thickness of boundary layer is 19 μm, and pencil is hard In the case of degree is for 2H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, and And observed a layer segregation phenomenon.
Embodiment 4
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (D) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use the polydimethylsiloxane (Mw:1900) of 776g methyl methacrylate and 24g mono-sulfydryl end-blocking to substitute 792g methyl methacrylate and the polydimethylsiloxane (Mw:1670) of 8g dimercapto end-blocking.
The difference of the surface energy between described first resin and the second resin (D) is 12mN/m, and the difference of melt viscosity is 330pa*s, the glass transition temperature of the second resin (D) is 103 DEG C, GPC the weight average molecular weight recording the second resin (D) is 100K, polydispersity index (PDI) is 2.3.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 4 that thickness is 3200 μm, difference is: make With described second resin (D).In this sample, the thickness of the second resin bed is 45 μm, and the thickness of boundary layer is 33 μm, and pencil is hard In the case of degree is for 2H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, and And observed a layer segregation phenomenon.
Embodiment 5
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (E) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use 576g methyl methacrylate, 200g cyclohexyl methacrylate and the poly-diformazan of 24g dimercapto end-blocking Radical siloxane (Mw:1670) substitute 792g methyl methacrylate and 8g dimercapto end-blocking polydimethylsiloxane (Mw: 1670)。
The difference of the surface energy between described first resin and the second resin (E) is 17mN/m, and the difference of melt viscosity is 470pa*s, the glass transition temperature of the second resin (E) is 96 DEG C, GPC the weight average molecular weight recording the second resin (E) is 100K, polydispersity index (PDI) is 2.1.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 5 that thickness is 3200 μm, difference is: make With described second resin (E).In this sample, the thickness of the second resin bed is 49 μm, and the thickness of boundary layer is 35 μm, and pencil is hard In the case of degree is for 2.5H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, And observed a layer segregation phenomenon.
Embodiment 6
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (F) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use 576g methyl methacrylate, 200g phenyl methacrylate and the poly dimethyl of 24g dimercapto end-blocking Siloxanes (Mw:1670) substitutes 792g methyl methacrylate and the polydimethylsiloxane (Mw:1670) of 8g dimercapto end-blocking.
The difference of the surface energy between described first resin and the second resin (F) is 20mN/m, and the difference of melt viscosity is 455pa*s, the glass transition temperature of the second resin (F) is 102 DEG C, GPC the weight average molecular weight recording the second resin (F) is 100K, polydispersity index (PDI) is 2.1.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 6 that thickness is 3200 μm, difference is: make With described second resin (F).In this sample, the thickness of the second resin bed is 50 μm, and the thickness of boundary layer is 32 μm, and pencil is hard In the case of degree is for 2.5H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, And observed a layer segregation phenomenon.Peak strength ratio [IBD(C=C)/IA(C=O) meansigma methods] is 0.0121, standard deviation It is 0.0005；Peak strength ratio [IBD(outside face)/IA(C=O) meansigma methods] is 0.413, and standard deviation is 0.0029；Above-mentioned number Value is measured by infrared spectrophotometer.
Embodiment 7
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (G) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use 536g methyl methacrylate, 120g acrylamide, 120g hydroxyethyl methylacrylate and 24g bis-mercapto The polydimethylsiloxane (Mw:1670) of base end-blocking substitutes 792g methyl methacrylate and the poly dimethyl of 8g dimercapto end-blocking Siloxanes (Mw:1670).
The difference of the surface energy between described first resin and the second resin (G) is 6mN/m, and the difference of melt viscosity is 395pa* S, the glass transition temperature of the second resin (G) is 122 DEG C, GPC the weight average molecular weight recording the second resin (G) is 100K, Polydispersity index (PDI) is 1.9.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 7 that thickness is 3200 μm, difference is: make With described second resin (G).In this sample, the thickness of the second resin bed is 65 μm, and the thickness of boundary layer is 28 μm, and pencil is hard In the case of degree is for 1.5H, at IZOD1/8 " in the case of intensity be 7kg*cm/cm, at IZOD1/4 ", intensity is 7kg*cm/cm, And observed a layer segregation phenomenon.
Embodiment 8
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (H) uses to be prepared, no with the same procedure described in embodiment 1 It is with part: use 536g methyl methacrylate, 240g hydroxyethyl methylacrylate and the poly-diformazan of 24g dimercapto end-blocking Radical siloxane (Mw:1670) substitute 792g methyl methacrylate and 8g dimercapto end-blocking polydimethylsiloxane (Mw: 1670)。
The difference of the surface energy between described first resin and the second resin (H) is 7mN/m, and the difference of melt viscosity is 450pa* S, the glass transition temperature of the second resin (H) is 108 DEG C, GPC the weight average molecular weight recording the second resin (H) is 100K, Polydispersity index (PDI) is 1.9.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 8 that thickness is 3200 μm, difference is: make With described second resin (H).In this sample, the thickness of the second resin bed is 54 μm, and the thickness of boundary layer is 30 μm, and pencil is hard In the case of degree is for 2H, at IZOD1/8 " in the case of intensity be 9kg*cm/cm, at IZOD1/4 ", intensity is 9kg*cm/cm, and And observed a layer segregation phenomenon.
Embodiment 9
The preparation of (1) first and second resin and the measurement of physical property
First resin is same as in Example 1, and the second resin (I) uses to be prepared, no with the same procedure described in embodiment 1 Be with part: use 536g methyl methacrylate, 120g vinyl pyrrolidone, 120g hydroxyethyl methylacrylate and Polydimethylsiloxane (Mw:1670) the replacement 792g methyl methacrylate of 24g dimercapto end-blocking and 8g dimercapto block Polydimethylsiloxane (Mw:1670).
The difference of the surface energy between described first resin and the second resin (I) is 6mN/m, and the difference of melt viscosity is 410pa* S, the glass transition temperature of the second resin (I) is 110 DEG C, GPC the weight average molecular weight recording the second resin (I) is 100K, Polydispersity index (PDI) is 2.2.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 9 that thickness is 3200 μm, difference is: make With described second resin (I).In this sample, the thickness of the second resin bed is 62 μm, and the thickness of boundary layer is 32 μm, and pencil is hard In the case of degree is for 2H, at IZOD1/8 " in the case of intensity be 8kg*cm/cm, at IZOD1/4 ", intensity is 8kg*cm/cm, and And observed a layer segregation phenomenon.
Comparative example 1
By 100 weight portions, the resin particle of the first identical resin used is dried in an oven with embodiment 1, and passes through This resin particle being dried at 240 DEG C of hemostasis, is prepared the sample 10 that thickness is 3200 μm by EC100 Φ 30 syringe (ENGEL).
The result of the physical property measuring the sample 10 of above-mentioned preparation is, glass transition temperature (Tg) is 70 DEG C, In the case of IZOD1/8 " in the case of intensity be 10kg*cm/cm, at IZOD1/4 ", intensity is 10kg*cm/cm, pencil hardness For F.
Comparative example 2
The first identical resin used with embodiment 1 is used to use and embodiment as the first resin, the second resin (J) Prepared by the same procedure described in 1, difference is: it is poly-that use 640g methyl methacrylate and 160g dimercapto block Dimethyl siloxane (Mw:1670) substitute 792g methyl methacrylate and 8g dimercapto end-blocking polydimethylsiloxane (Mw: 1670)。
The difference of the surface energy between described first resin and the second resin (J) is 22mN/m, and the difference of melt viscosity is 620pa*s, the glass transition temperature of the second resin (J) is 45 DEG C, GPC the weight average molecular weight recording the second resin (J) is 100K, polydispersity index (PDI) is 4.2.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 11 that thickness is 3200 μm, difference is: make With described second resin (J).In this sample, owing to sample is peeling-off and a layer segregation phenomenon cannot be observed, nor Pencil hardness can be measured.It addition, for thickness, the second resin bed or boundary layer all cannot be carried out measuring.At IZOD1/ 8 " in the case of, intensity is 3kg*cm/cm, at IZOD1/4 " in the case of intensity be 2kg*cm/cm.
Comparative example 3
Use and the first resin identical used by embodiment 1 is as the first resin, and by polymethyl methacrylate (LGMMA IF870) is used as the second resin.The difference of surface energy, the difference of melt viscosity is not had between first and second resin described For 270pa*s, and the glass transition temperature of the second resin is 104 DEG C.The weight average molecular weight being recorded this second resin by GPC is 73K, polydispersity index is 1.9.
(2) preparation of resin blend and the measurement of physical property
Using and prepare, with the same procedure described in embodiment 1, the sample 13 that thickness is 3200 μm, difference is: make Use described polymethyl methacrylate.In this sample, do not observe a layer segregation phenomenon.It addition, for thickness, no matter Two resin beds or boundary layer all cannot be carried out measuring.Pencil hardness is H.At IZOD1/8 " in the case of intensity be 5.2kg*cm/ Cm, at IZOD1/4 " in the case of intensity be 4.9kg*cm/cm.
Comparative example 4
By 100 weight portions, the resin particle of the first identical resin used is dried in an oven with embodiment 1, and passes through This resin particle being dried at 240 DEG C of hemostasis, is prepared sample by EC100 Φ 30 syringe (ENGEL).
Form hard coat film by the following method: use Mayer rod #9, be coated with on to the sample homemade comprise multifunctional Resistant hard coat film solution (dipentaerythritol acrylate (DPHA) of 17.5wt%, the Ji Wusi of 10wt% of acrylate Alcohol triacrylate (PETA), the perfluoro hexyl ethylmethyl acrylate of 1.5wt%, 5wt% urethane acrylate (by The EB1290 that SK Cytech produces), the methyl ethyl ketone of 45wt%, the isopropanol of 20wt% and the uv initiator of 1wt% (IRGACURE184 produced by Ciba)) and form film, this film is dried 4 minutes at 60 to 90 DEG C, and by by intensity For 3,000mJ/cm2Ultraviolet radiation and make this coating solution compositions solidify.
The pencil hardness of above-mentioned hard coat film is 3H, and the peak strength ratio [I measured by infrared spectrophotometerBD(C= C)/IA] and [I (C=O)BD(outside face)/IA(C=O) meansigma methods and standard deviation] are 0.

Claims (18)

1. a resin blend, comprises:
First resin；With
Second resin, described second resin in main chain containing the hydrophobic part that represented by chemical formula 1, and with described first tree The difference of fat surface energy at 25 DEG C is 0.1 to 20mN/m,
Wherein, described second resin is the monomer the comprising chemical formula 2 expression polymer as polymerized unit, and
Wherein, this resin blend can form hierarchy during melt-processed:
In chemical formula 1 and chemical formula 2, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is 1 to 100 Number, X1And X2For hydrogen, alkyl containing 1 to 16 carbon atom or sulfydryl (-SH), and X1And X2In at least one be sulfydryl.
Resin blend the most according to claim 1, wherein, at 100 to 1000s-1Shear rate and this resin alloy Under the processing temperature of thing, the difference of the melt viscosity between described first resin and described second resin is 0.1 to 3000pa*s.
Resin blend the most according to claim 1, wherein, the glass transition temperature of described second resin is higher than described The difference of the glass transition temperature between the glass transition temperature of the first resin, and this first resin and second resin is 10 To 150 DEG C.
Resin blend the most according to claim 1, wherein, the polydispersity index of described second resin is 1 to 2.5.
Resin blend the most according to claim 1, wherein, the weight average molecular weight of described second resin be 30,000 to 200,000。
Resin blend the most according to claim 1, wherein, described second resins based on 100 weight portions, described by changing The content of the hydrophobic part that formula 1 represents is 0.01 to 15 weight portion.
Resin blend the most according to claim 1, wherein, described second resin also comprises selected from containing 2 to 20 carbon The alkyl of atom, the alicyclic ring containing 5 to 40 carbon atoms and containing 6 to 40 carbon atoms aromatic ring at least one organic official Can group.
Resin blend the most according to claim 1, wherein, described second resin also comprises and combines the donor of hydrogen and be subject to Body.
Resin blend the most according to claim 1, wherein, described first resin includes selected from styrene resin, gathers Olefine kind resin, polyoxyalkylene resinoid, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyphenylene sulfide ethers At least one in resin, vinyl alcohol resin, acrylic resin and their copolymer.
Resin blend the most according to claim 1, wherein, described second resin includes selected from (methyl) acrylate In resinoid, epoxylite, oxetanes resinoid, isocyanates resinoid, fluorine-type resin and their copolymer At least one.
11. 1 kinds of resin particles with hierarchy, including:
Core containing the first resin；With
Containing the shell of the second resin, described second resin in main chain containing the hydrophobic part that represented by chemical formula 1, and with institute The difference stating first resin surface energy at 25 DEG C is 0.1 to 20mN/m, and
Wherein, described second resin is the monomer the comprising chemical formula 2 expression polymer as polymerized unit,
Wherein, this resin particle can form hierarchy during melt-processed:
In chemical formula 1 and chemical formula 2, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is 1 to 100 Number, X1And X2For hydrogen, alkyl containing 1 to 16 carbon atom or sulfydryl (-SH), and X1And X2In at least one be sulfydryl.
12. 1 kinds of methods preparing resin formed article, including:
Make the resin blend described in claim 1 melt, form mixture of melts；With
Described mixture of melts is processed, forms hierarchy.
13. methods according to claim 12, also include: solidify the hierarchy of described resin blend.
14. methods according to claim 12, wherein, described melted and processing is carried out under shear stress.
15. methods according to claim 13, wherein, described in be cured as heat cure or ultraviolet curing.
16. 1 kinds of methods preparing resin formed article, including:
Make the resin particle described in claim 11 melt, form mixture of melts；With
Described mixture of melts is processed, forms hierarchy.
17. 1 kinds of resin formed articles with hierarchy, including:
The first resin bed containing the first resin；
Containing the second resin bed of the second resin, this second resin bed is formed on the first resin bed；With
Boundary layer, this boundary layer contains described first resin and the second resin, and the first resin bed and the second resin bed it Between formed,
Wherein, described hierarchy is during comprising the melt-processed of resin blend of described first resin and the second resin Formed,
Wherein, described second resin contains the hydrophobic part represented by chemical formula 1 in main chain, and
Described second resin is the monomer the comprising chemical formula 2 expression polymer as polymerized unit:
In chemical formula 1 and chemical formula 2, RaTo RdBeing each independently the alkyl containing 1 to 16 carbon atom, n is 1 to 100 Number, X1And X2For hydrogen, alkyl containing 1 to 16 carbon atom or sulfydryl (-SH), and X1And X2In at least one be sulfydryl.
18. resin formed articles according to claim 17, wherein, by infrared spectrophotometer at the table of the second resin bed The component of the first resin bed is detected on face.
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